JP2016177260A - Hard coat laminate film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hard coat laminate film excellent in transparency, surface hardness, bending resistance, scratch resistance, tone and surface appearance, and suitable as a member of an image display device such as a liquid crystal display, a plasma display and an electroluminescence display, particularly as a display surface plate of an image display device having a touch panel function.SOLUTION: The hard coat laminate film includes layers of, from a surface side, a first hard coat, a second hard coat, and a transparent resin film. The first hard coat is formed of a coating material containing no inorganic particles, while the second hard coat is formed of a coating material containing inorganic particles. The hard coat laminate satisfies the following conditions: (1) the total ray transmittance of the laminate is 85% or more; and (2) the surface of the first hard coat shows a pencil hardness scale of 5H or higher, preferably 7H or higher.SELECTED DRAWING: Figure 2

Description

The present invention relates to a hard coat laminated film. More specifically, the present invention relates to a hard coat laminated film excellent in transparency, surface hardness, bending resistance, scratch resistance, color tone, and surface appearance.

In recent years, touch panels that are installed on image display devices such as a liquid crystal display, a plasma display, and an electroluminescence display and can be input by touching with a finger or a pen while watching the display have become widespread.

Conventionally, glass-based articles have been used for display faceplates of touch panels because they meet required characteristics such as heat resistance, dimensional stability, high transparency, high surface hardness, and high rigidity. On the other hand, glass has problems such as low impact resistance and easy cracking; low workability; difficult to handle; high specific gravity and heavy; difficult to meet demands for curved display and flexibility. Therefore, materials that replace glass have been actively studied, and hard coats with excellent surface hardness and scratch resistance on the surface of transparent resin films such as triacetylcellulose, polyethylene terephthalate, polycarbonate, polymethyl methacrylate, and norbornene polymers. A large number of hard coat laminated films formed with a film have been proposed (for example, Patent Documents 1 and 2). However, its scratch resistance is still insufficient, and there is a need for a hard coat laminated film that can maintain surface characteristics such as slipperiness even when repeatedly wiped with a handkerchief or the like.

Japanese Patent Laid-Open No. 2000-052472 JP 2000-214791 A

An object of the present invention is excellent in transparency, surface hardness, bending resistance, scratch resistance, color tone, and surface appearance, and is a member of an image display device such as a liquid crystal display, a plasma display, and an electroluminescence display (touch panel function). Including an image display device having an image display device and an image display device not having a touch panel function.), In particular, to provide a hard coat laminated film suitable as a display face plate of an image display device having a touch panel function.

As a result of intensive studies, the present inventor has found that the above-described problems can be achieved by a specific hard coat laminated film.

That is, the present invention
The first hard coat, the second hard coat, and the transparent resin film layer in order from the surface side,
The first hard coat is made of a coating containing no inorganic particles;
The second hard coat is made of a coating containing inorganic particles;
It is a hard coat laminated film satisfying the following (a) and (b).
(A) The total light transmittance is 85% or more.
(B) The pencil hardness of the first hard coat surface is 5H or more.

2nd invention is a hard coat laminated film as described in 1st invention whose pencil hardness of the said 1st hard coat surface is 7H or more.

The third invention is the hard coat laminated film according to the first invention or the second invention which further satisfies the following (c) and (d).
(C) Haze is 2.0% or less.
(D) The minimum bending radius is 40 mm or less.

The fourth invention is the hard coat laminated film according to any one of the first to third inventions that further satisfies the following (e) and (f).
(E) The water contact angle on the surface of the first hard coat is 100 degrees or more.
(F) The water contact angle after 20,000 swabs on the first hard coat surface is 100 degrees or more.

According to a fifth aspect of the present invention, the transparent resin film comprises a first poly (meth) acrylimide resin layer (α1); an aromatic polycarbonate resin layer (β); a second poly (meth) acrylimide resin layer (α2). Is a hard coat laminated film according to any one of the first to fourth inventions, which are transparent multilayer films laminated in this order.

6th invention consists of a coating material in which the said 1st hard coat contains a silane coupling agent; It is a hard coat laminated film in any one of 1st-5th invention.

A seventh invention is the hard coat laminated film according to any one of the first to sixth inventions, wherein the thickness of the first hard coat is 0.5 to 5 μm.

An eighth invention is the hard coat laminated film according to any one of the first to seventh inventions, wherein the thickness of the second hard coat is 15 to 30 μm.

A ninth invention is the use of the hard coat laminated film according to any one of the first to eighth inventions as an image display device member.

A tenth invention is an image display device including the hard coat laminated film according to any one of the first to eighth inventions.

The hard coat laminated film of the present invention is excellent in transparency, surface hardness, bending resistance, scratch resistance, color tone, and surface appearance. Therefore, members of an image display device such as a liquid crystal display, a plasma display, and an electroluminescence display (including an image display device having a touch panel function and an image display device not having a touch panel function), particularly an image display device having a touch panel function. It can be suitably used as a display face plate.

The hard coat laminated film of the present invention has a first hard coat layer, a second hard coat layer, and a transparent resin film layer in order from the surface side, and the first hard coat is made of a paint containing no inorganic particles; 2 Hard coat consists of the coating material containing an inorganic particle.

Inorganic particles (for example, silica (silicon dioxide); metal oxide particles such as aluminum oxide, zirconia, titania, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide, antimony oxide, cerium oxide; magnesium fluoride , Metal fluoride particles such as sodium fluoride; metal sulfide particles; metal nitride particles; and metal particles; etc.) are highly effective in increasing the hardness of the hard coat. On the other hand, the interaction with the resin component of the paint was weak, which caused the scratch resistance to be insufficient. Therefore, in the present invention, the first hard coat forming the outermost surface does not contain inorganic particles to maintain scratch resistance, while the second hard coat has inorganic particles, preferably an average particle diameter of 1 This problem is solved by increasing the hardness by including inorganic fine particles of ˜300 nm.

Here, “does not contain” inorganic particles means that it does not contain a significant amount of inorganic particles. In the field of hard coat forming paints, the significant amount of inorganic particles is usually about 1 part by mass or more with respect to 100 parts by mass of the resin component of the paint. Therefore, “does not contain” inorganic particles means that the amount of inorganic particles is usually less than 1 part by weight, preferably 0.1 parts by weight or less, more preferably 0.01 parts by weight with respect to 100 parts by weight of the resin component of the paint. It can be paraphrased as part or less.

Here, “containing” inorganic particles means that the particles contain a significant amount of inorganic particles to increase the hardness of the hard coat. In the field of hard coat forming paints, a significant amount for increasing the hardness of the hard coat is usually about 5 parts by mass or more with respect to 100 parts by mass of the resin component of the paint. Therefore, “including” the inorganic particles means that the amount of the inorganic particles is usually 5 parts by mass or more, preferably 15 parts by mass or more, more preferably 30 parts by mass or more, and still more preferably 100 parts by mass of the resin component of the paint. Can be paraphrased as 50 parts by mass or more.

The hard coat laminated film of the present invention has a total light transmittance (measured using a turbidimeter “NDH2000 (trade name)” of Nippon Denshoku Industries Co., Ltd. according to JIS K 7361-1: 1997) of 85% or more. , Preferably 88% or more, more preferably 90% or more. When the total light transmittance is 85% or more, the hard coat laminated film of the present invention can be suitably used as an image display device member. A higher total light transmittance is preferable.

The hard coat laminated film of the present invention has a haze (measured according to JIS K 7136: 2000 using a turbidimeter “NDH2000 (trade name)” manufactured by Nippon Denshoku Industries Co., Ltd.) of 2.0% or less, preferably It is 1.5% or less, more preferably 1.0% or less, still more preferably 0.5% or less. When the haze is 2.0% or less, the hard coat laminated film of the present invention can be suitably used as an image display device member. The lower the haze, the better.

The hard coat laminated film of the present invention uses a pencil “Uni (trade name)” manufactured by Mitsubishi Pencil Co., Ltd. under the condition of 750 g load according to JIS K 5600-5-4. The measurement is 5H or higher, preferably 6H or higher, more preferably 7H or higher. When the pencil hardness is 5H or more, the hard coat laminated film of the present invention can be suitably used as an image display device member. Higher pencil hardness is preferable.

The hard coat laminated film of the present invention has a minimum bending radius of preferably 40 mm or less, more preferably 35 mm or less, and further preferably 30 mm or less. When the minimum bending radius is preferably 40 mm or less, the hard coat laminated film of the present invention can be easily handled as a film roll, which is advantageous in terms of production efficiency. The smaller the minimum bending radius, the better. Here, the minimum bending radius is a value measured according to the test (d) of the following example.

The minimum bend radius is a bend radius immediately before a crack is generated on the surface of the bent portion when the hard coat laminated film is bent, and is an index indicating the limit of bending. The bending radius is defined in the same way as the curvature radius.

The radius of curvature is defined as follows. The length from the M point to the N point of the curve is ΔS; the difference between the slope of the tangent at the M point and the slope of the tangent at the N point is Δα; a straight line perpendicular to the tangent at the M point and intersecting at the M point When the intersection point with a straight line that is perpendicular to the tangent line at the N point and intersects at the N point is O; and when ΔS is sufficiently small, the curve from the M point to the N point can be approximated to an arc. (Figure 3). The radius at this time is defined as the radius of curvature. When the radius of curvature is R, ∠MON = Δα, and when ΔS is sufficiently small, Δα is also sufficiently small, so ΔS = RΔα is established, and R = ΔS / Δα.

In the hard coat laminated film of the present invention, the water contact angle on the surface of the first hard coat is preferably 100 degrees or more, more preferably 105 degrees or more. When the hard coat laminated film of the present invention is used as a display face plate of a touch panel, the first hard coat forms a touch surface. When the water contact angle on the surface of the first hard coat is 100 degrees or more, the touch panel can be operated by sliding a finger or a pen as desired on the touch surface. From the viewpoint of sliding a finger or pen as desired, a higher water contact angle is preferable, and there is no particular upper limit for the water contact angle, but from the viewpoint of slipperiness, about 120 degrees is usually sufficient. Here, the water contact angle is a value measured according to the test (e) in the following Examples.

The hard coat laminated film of the present invention preferably has a water contact angle of 100 degrees or more after 20,000 cotton swabs on the first hard coat surface. More preferably, the water contact angle after reciprocating 25,000 cotton swabs is 100 degrees or more. When the water contact angle after 20,000 cotton reciprocations is 100 degrees or more, it is possible to maintain surface characteristics such as slipperiness even when repeatedly wiped with a handkerchief or the like. The larger the number of cotton wipes that can maintain a water contact angle of 100 degrees or more, the better. Here, the water contact angle after cotton wiping is a value measured according to the test (f) of the following examples.

The yellowness index of the hard coat laminated film of the present invention (measured using a color meter “SolidSpec-3700 (trade name)” manufactured by Shimadzu Corporation in accordance with JIS K 7105: 1981) is preferably 3 or less. Preferably it is 2 or less, More preferably, it is 1 or less. The lower the yellowness index, the better. It can be suitably used as an image display device member.

First hard coat:
The first hard coat forms the surface of the hard coat laminated film of the present invention. The first hard coat forms a touch surface when the hard coat laminated film of the present invention is used as a display face plate of an image display device having a touch panel function. The first hard coat exhibits good scratch resistance and functions to maintain surface characteristics such as slipperiness even when repeatedly wiped with a handkerchief or the like.

The first hard coat forming paint is not limited except that it does not contain inorganic particles, and any paint can be used. Preferred examples of the first hard coat-forming coating material include an active energy ray-curable resin that can be polymerized and cured by active energy rays such as ultraviolet rays and electron beams to form a hard coat. Can do.

Examples of the active energy ray-curable resin include polyurethane (meth) acrylate, polyester (meth) acrylate, polyacryl (meth) acrylate, epoxy (meth) acrylate, polyalkylene glycol poly (meth) acrylate, and polyether. (Meth) acryloyl group-containing prepolymer or oligomer such as (meth) acrylate; methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate , Lauryl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, phenyl (meth) acrylate Phenyl cellosolve (meth) acrylate, 2-methoxyethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2-acryloyloxyethyl hydrogen phthalate, dimethylaminoethyl (meth) acrylate, trifluoroethyl ( (Meth) acrylate and (meth) acryloyl group-containing monofunctional reactive monomers such as trimethylsiloxyethyl methacrylate; monofunctional reactive monomers such as N-vinylpyrrolidone and styrene; diethylene glycol di (meth) acrylate, neopentyl glycol di ( (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 2,2′-bis (4- (meth) acrylo (Methoxy) acryloyl group-containing bifunctional reactive monomers such as 2,2′-bis (4- (meth) acryloyloxypolypropyleneoxyphenyl) propane; trimethylolpropane tri (meth) (Meth) acryloyl group-containing trifunctional reactive monomers such as acrylate and trimethylolethane tri (meth) acrylate; (meth) acryloyl group-containing tetrafunctional reactive monomers such as pentaerythritol tetra (meth) acrylate; and dipenta Examples of the resin include one or more selected from (meth) acryloyl group-containing hexafunctional reactive monomers such as erythritol hexaacrylate, or resins having one or more of the above as constituent monomers. As said active energy ray curable resin, these 1 type, or 2 or more types of mixtures can be used. In the present specification, (meth) acrylate means acrylate or methacrylate.

When the hard coat laminated film of the present invention is used as a member of an image display device, particularly a display face plate of an image display device having a touch panel function, transparency, color tone, scratch resistance, surface hardness, bending resistance, and surface From the viewpoint of appearance, the first hard coat-forming coating material includes (A) polyfunctional (meth) acrylate 100 parts by mass; (B) water repellent 0.01 to 7 parts by mass; and (C) silane coupling. A coating material containing 0.01 to 10 parts by mass of an agent and not containing inorganic particles is preferable.

(A) Polyfunctional (meth) acrylate:
The component (A) is a (meth) acrylate having two or more (meth) acryloyl groups in one molecule, and has two or more (meth) acryloyl groups in one molecule. Polymerizes and cures with active energy rays to form a hard coat.

Examples of the polyfunctional (meth) acrylate include diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 2, (Meth) acryloyl group-containing bifunctional reaction such as 2′-bis (4- (meth) acryloyloxypolyethyleneoxyphenyl) propane and 2,2′-bis (4- (meth) acryloyloxypolypropyleneoxyphenyl) propane -Functional monomers; (meth) acryloyl group-containing trifunctional reactive monomers such as trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, and pentaerythritol tri (meth) acrylate; pentaerythritol (Meth) acryloyl group-containing tetrafunctional reactive monomers such as dimethyltetra (meth) acrylate; (meth) acryloyl group-containing hexafunctional reactive monomers such as dipentaerythritol hexaacrylate; A combination (oligomer or prepolymer) can be mentioned. As said component (A), these 1 type, or 2 or more types of mixtures can be used.

In the present specification, (meth) acrylate means acrylate or methacrylate.

(B) Water repellent:
The component (B) functions to increase slipperiness, dirt adhesion prevention, and dirt wiping.

Examples of the water repellent include wax-based water repellents such as paraffin wax, polyethylene wax, and acrylic / ethylene copolymer wax; silicon-based water repellents such as silicon oil, silicon resin, polydimethylsiloxane, and alkylalkoxysilane. Agents; fluorine-containing water repellents such as fluoropolyether water repellents and fluoropolyalkyl water repellents; and the like. As said component (B), these 1 type, or 2 or more types of mixtures can be used.

Among these, as the component (B), a fluoropolyether water repellent is preferable from the viewpoint of water repellent performance. From the viewpoint of preventing troubles such as a chemical bond or strong interaction between the component (A) and the component (B) and bleeding out of the component (B), the component (B) includes A water repellent containing a compound containing a (meth) acryloyl group and a fluoropolyether group (hereinafter abbreviated as a (meth) acryloyl group-containing fluoropolyether water repellent) is more preferable. More preferable as the component (B) is to appropriately adjust the chemical bond or interaction between the component (A) and the component (B), from the viewpoint of expressing good water repellency while maintaining high transparency. It is a mixture of an acryloyl group-containing fluoropolyether water repellent and a methacryloyl group-containing fluoropolyether water repellent.

The amount of the component (B) is usually 7 parts by mass or less, preferably 4 parts by mass with respect to 100 parts by mass of the component (A) from the viewpoint of preventing troubles such as bleeding out of the component (B). Part or less, more preferably 2 parts by weight or less. On the other hand, from the viewpoint of obtaining the effect of using the component (B), it is usually 0.01 parts by mass or more, preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more.

(C) Silane coupling agent:
The component (C) serves to improve the adhesion between the first hard coat and the second hard coat.

Silane coupling agents include hydrolyzable groups (for example, alkoxy groups such as methoxy group and ethoxy group; acyloxy groups such as acetoxy group; halogen groups such as chloro group; and the like) and organic functional groups (for example, amino groups, A silane compound having at least two different reactive groups such as a mercapto group, a vinyl group, an epoxy group, a methacryloxy group, an acryloxy group, and an isocyanate group. Among these, as the component (C), from the viewpoint of adhesion, a silane coupling agent having an amino group (a silane compound having an amino group and a hydrolyzable group) and a silane coupling agent having a mercapto group ( A silane compound having a mercapto group and a hydrolyzable group is preferred. From the viewpoint of adhesion and odor, a silane coupling agent having an amino group is more preferable.

Examples of the silane coupling agent having an amino group include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, and N-2. -(Aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, Examples thereof include N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane, and the like.

Examples of the silane coupling agent having a mercapto group include 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane.

As said component (C), these 1 type, or 2 or more types of mixtures can be used.

The compounding amount of the component (C) is usually 0.01 parts by mass or more, preferably 0.05 parts by mass or more, from the viewpoint of surely obtaining an adhesion improving effect with respect to 100 parts by mass of the component (A). More preferably, it is 0.1 mass part or more. On the other hand, from the viewpoint of the pot life of the paint, it may be usually 10 parts by mass or less, preferably 5 parts by mass or less, more preferably 1 part by mass or less.

From the viewpoint of improving the curability by active energy rays, the first hard coat-forming coating material has a compound having two or more isocyanate groups (—N═C═O) in one molecule and / or photopolymerization initiation. It is preferable to further contain an agent.

Examples of the compound having two or more isocyanate groups in one molecule include methylene bis-4-cyclohexyl isocyanate; trimethylolpropane adduct of tolylene diisocyanate, trimethylolpropane adduct of hexamethylene diisocyanate, trimethylol of isophorone diisocyanate. Polyisocyanates such as propane adduct, isocyanurate of tolylene diisocyanate, isocyanurate of hexamethylene diisocyanate, isocyanurate of isophorone diisocyanate, biuret of hexamethylene diisocyanate; and urethanes such as block isocyanates of the above polyisocyanates A crosslinking agent etc. can be mention | raise | lifted. As the compound having two or more isocyanate groups in one molecule, one or a mixture of two or more thereof can be used. Further, at the time of crosslinking, a catalyst such as dibutyltin dilaurate or dibutyltin diethylhexoate may be added as necessary.

Examples of the photopolymerization initiator include benzophenone, methyl-o-benzoylbenzoate, 4-methylbenzophenone, 4,4′-bis (diethylamino) benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl. Benzophenone compounds such as -4'-methyldiphenyl sulfide, 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; benzoin, benzoin methyl ether, benzoin Benzoin compounds such as ethyl ether, benzoin isopropyl ether and benzyl methyl ketal; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, etc. Acetophenone compounds; anthraquinone compounds such as methylanthraquinone, 2-ethylanthraquinone, 2-amylanthraquinone; thioxanthone compounds such as thioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone; alkylphenones such as acetophenone dimethyl ketal Compounds; triazine compounds; biimidazole compounds; acyl phosphine oxide compounds; titanocene compounds; oxime ester compounds; oxime phenylacetate compounds; hydroxy ketone compounds; and aminobenzoate compounds. it can. As the photopolymerization initiator, one or a mixture of two or more of these can be used.

The first hard coat-forming coating material includes, as desired, an antistatic agent, a surfactant, a leveling agent, a thixotropic agent, a stain-preventing agent, a printability improving agent, an antioxidant, a weathering stabilizer, One or more additives such as a light resistance stabilizer, an ultraviolet absorber, a heat stabilizer, organic fine particles, and an organic colorant can be contained.

The first hard coat-forming coating material may contain a solvent as desired in order to dilute to a concentration that facilitates coating. The solvent is not particularly limited as long as it does not react with the above components (A) to (C) and other optional components or catalyze (promote) the self-reaction (including degradation reaction) of these components. Not. Examples of the solvent include 1-methoxy-2-propanol, ethyl acetate, nbutyl acetate, toluene, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, and acetone. As said solvent, these 1 type, or 2 or more types of mixtures can be used.

The said 1st hard-coat formation coating material can be obtained by mixing and stirring these components.

The method for forming the first hard coat using the first hard coat forming paint is not particularly limited, and a known web coating method can be used. Specifically, methods such as roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, and die coating can be used.

The thickness of the first hard coat is preferably 0.5 μm or more, more preferably 1 μm or more from the viewpoint of scratch resistance and hardness. On the other hand, from the viewpoint of hardness and adhesion to the second hard coat, it is preferably 5 μm or less, more preferably 4 μm or less, and even more preferably 3 μm or less.

Second hard coat The second hard coat-forming paint is not limited except that it contains inorganic particles, and any paint can be used. Preferred examples of the second hard coat-forming coating material further include a coating material that contains an active energy ray-curable resin and that can be polymerized and cured by active energy rays such as ultraviolet rays and electron beams to form a hard coat. be able to.

The active energy ray-curable resin is described above in the description of the first hard coat forming coating material. As said active energy ray curable resin, these 1 type, or 2 or more types of mixtures can be used.

When the hard coat laminated film of the present invention is used as a member of an image display device, particularly a display face plate of an image display device having a touch panel function, transparency, color tone, scratch resistance, surface hardness, bending resistance, and surface From the viewpoint of appearance, the second hard coat forming coating composition includes (A) 100 parts by mass of polyfunctional (meth) acrylate; and (D) 50 to 300 parts by mass of inorganic fine particles having an average particle size of 1 to 300 nm. Paint is preferred.

Said (A) polyfunctional (meth) acrylate was mentioned above in description of the said coating material for 1st hard-coat formation. As said component (A), these 1 type, or 2 or more types of mixtures can be used.

(D) Inorganic fine particles having an average particle size of 1 to 300 nm:
The component (D) functions to dramatically increase the hardness of the hard coat laminated film of the present invention.

Examples of the inorganic fine particles include silica (silicon dioxide); metal oxide fine particles such as aluminum oxide, zirconia, titania, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide, antimony oxide, and cerium oxide; Examples thereof include metal fluoride fine particles such as magnesium fluoride and sodium fluoride; metal sulfide fine particles; metal nitride fine particles; and metal fine particles.

Among these, in order to obtain a hard coat having higher surface hardness, fine particles of silica or aluminum oxide are preferable, and fine particles of silica are more preferable. Examples of commercially available silica fine particles include Snowtex (trade name) manufactured by Nissan Chemical Industries, Ltd., Quartron (trade name) manufactured by Fuso Chemical Industries, Ltd., and the like.

For the purpose of increasing the dispersibility of the inorganic fine particles in the paint or increasing the surface hardness of the obtained hard coat, the surface of the inorganic fine particles is treated with a silane coupling agent such as vinylsilane or aminosilane; a titanate coupling agent. An aluminate coupling agent; an organic compound having a reactive functional group such as an ethylenically unsaturated bond group such as a (meth) acryloyl group, a vinyl group, and an allyl group; and an epoxy group; and a fatty acid, a fatty acid metal salt, etc. It is preferable to use a material treated with a surface treatment agent or the like.

The average particle size of the component (D) is 300 nm or less, preferably 200 nm or less, and more preferably 120 nm or less, from the viewpoint of maintaining the transparency of the hard coat and ensuring the effect of improving the hardness. On the other hand, there is no particular lower limit on the average particle diameter, but normally available inorganic fine particles are fine at most about 1 nm.

In the present specification, the average particle size of the inorganic fine particles is the particle size distribution curve measured using a laser diffraction / scattering particle size analyzer “MT3200II (trade name)” manufactured by Nikkiso Co., Ltd. Is the particle diameter at which the accumulation of 50% by mass.

The compounding amount of the component (D) is 50 parts by mass or more, preferably 80 parts by mass or more from the viewpoint of surface hardness with respect to 100 parts by mass of the component (A). On the other hand, from the viewpoint of transparency, it is 300 parts by mass or less, preferably 200 parts by mass or less, more preferably 160 parts by mass or less.

(E) Leveling agent:
From the viewpoint of making the surface of the second hard coat smooth and facilitating the formation of the first hard coat, it is preferable that the second hard coat forming coating material further contains (E) a leveling agent.

Examples of the leveling agent include acrylic leveling agents, silicon leveling agents, fluorine leveling agents, silicon / acrylic copolymer leveling agents, fluorine-modified acrylic leveling agents, fluorine-modified silicon leveling agents, and functionalities thereof. Leveling agents and the like into which groups (for example, alkoxy groups such as methoxy group and ethoxy group, acyloxy groups, halogen groups, amino groups, vinyl groups, epoxy groups, methacryloxy groups, acryloxy groups, and isocyanate groups) are introduced. Can do. Among these, the component (E) is preferably a silicon / acrylic copolymer leveling agent. As said component (E), these 1 type, or 2 or more types of mixtures can be used.

The blending amount of the component (E) is usually 0 from the viewpoint of making the surface of the second hard coat smooth and easily forming the first hard coat with respect to 100 parts by mass of the component (A). 0.01 parts by mass or more, preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more. On the other hand, from the viewpoint of allowing the first hard coat-forming coating material to be satisfactorily applied without being repelled on the second hard coat, it is 1 part by mass or less, preferably 0.6 parts by mass or less, and more. Preferably it may be 0.4 parts by mass or less.

From the viewpoint of improving the curability by active energy rays, the second hard coat-forming coating compound has a compound having two or more isocyanate groups (—N═C═O) in one molecule and / or photopolymerization initiation. It is preferable to further contain an agent.

The compound having two or more isocyanate groups in one molecule is described above in the description of the first hard coat-forming coating material. As the compound having two or more isocyanate groups in one molecule, one or a mixture of two or more thereof can be used.

The photopolymerization initiator is described above in the description of the first hard coat forming coating material. As the photopolymerization initiator, one or a mixture of two or more of these can be used.

For the second hard coat forming coating, an antistatic agent, a surfactant, a thixotropic agent, a stain inhibitor, a printability improver, an antioxidant, a weather resistance stabilizer, and a light resistance stability are optionally added. One or more additives such as an agent, an ultraviolet absorber, a heat stabilizer, a colorant, and organic fine particles can be contained.

The second hard coat-forming coating material may contain a solvent as desired in order to dilute to a concentration that facilitates coating. If the said solvent does not react with the said component (A), the said component (D), and other arbitrary components, or does not catalyze (promote) the self-reaction (including deterioration reaction) of these components, There is no particular limitation. Examples of the solvent include 1-methoxy-2-propanol, ethyl acetate, nbutyl acetate, toluene, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, and acetone. Of these, 1-methoxy-2-propanol is preferred. As said solvent, these 1 type, or 2 or more types of mixtures can be used.

The second hard coat-forming coating material can be obtained by mixing and stirring these components.

The method for forming the second hard coat using the second hard coat forming paint is not particularly limited, and a known web coating method can be used. Specifically, methods such as roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, and die coating can be used.

The thickness of the second hard coat is preferably 10 μm or more, more preferably 15 μm or more, and still more preferably 18 μm or more from the viewpoint of hardness. On the other hand, from the viewpoint of curling resistance and bending resistance, it is preferably 30 μm or less, more preferably 27 μm or less, and still more preferably 25 μm or less.

Transparent resin film:
The said transparent resin film is a layer used as the transparent film base material for forming the said 1st hard coat and the said 2nd hard coat on it. The transparent resin film is not limited except that it has high transparency and is not colored, and any transparent resin film can be used. For example, cellulose ester resins such as triacetyl cellulose; polyester resins such as polyethylene terephthalate; cyclic hydrocarbon resins such as ethylene norbornene copolymers; acrylic resins such as polymethyl methacrylate and polyethyl methacrylate; (Meth) acrylimide resin; aromatic polycarbonate resin; polyolefin resin such as polypropylene and 4-methyl-pentene-1; polyamide resin; polyarylate resin; polymer urethane acrylate resin; and polyimide resin And so on. These films include unstretched films, uniaxially stretched films, and biaxially stretched films. Moreover, these films include the laminated film which laminated | stacked these 1 type (s) or 2 or more types in two or more layers.

The thickness of the transparent resin film is not particularly limited, and can be any thickness as desired. From the viewpoint of handleability of the hard coat laminated film of the present invention, it may be usually 20 μm or more, preferably 50 μm or more. When the hard coat laminated film of the present invention is used for an application that does not require high rigidity, it may be usually 250 μm or less, preferably 150 μm or less from the viewpoint of economy. When the hard coat laminated film of the present invention is used as a display face plate of a touch panel, it may be usually 100 μm or more, preferably 200 μm or more, more preferably 300 μm or more from the viewpoint of maintaining rigidity. Moreover, from a viewpoint of meeting the request | requirement of thickness reduction of a touchscreen, it may be 1500 micrometers or less normally, Preferably it is 1200 micrometers or less, More preferably, it may be 1000 micrometers or less.

The transparent resin film is preferably a poly (meth) acrylimide resin film. It becomes a hard coat laminated film excellent in surface hardness, scratch resistance, transparency, surface smoothness, appearance, rigidity, heat resistance, and dimensional stability, and can be suitably used as a display face plate of a touch panel or a transparent conductive substrate. .

The above poly (meth) acrylimide resin introduces the characteristics of excellent heat resistance and dimensional stability of polyimide resin while maintaining the characteristics of acrylic resin such as high transparency, high surface hardness and high rigidity. Is a thermoplastic resin that has improved the disadvantage of being colored reddish brown, and is disclosed in, for example, JP-T-2011-519999. In the present specification, poly (meth) acrylimide means polyacrylimide or polymethacrylamide.

As said poly (meth) acrylimide-type resin, from the objective of using a hard coat laminated film for optical articles, such as a touch panel, it is not restrict | limited except having high transparency and a thing without coloring, arbitrary Poly (meth) acrylimide resin can be used.

A preferable example of the poly (meth) acrylimide resin is a yellowness index (measured according to JIS K 7105: 1981 using a chromaticity meter “SolidSpec-3700 (trade name)” manufactured by Shimadzu Corporation). 3 or less can be mentioned. The yellowness index is more preferably 2 or less, and even more preferably 1 or less. From the viewpoint of the extrusion load and the stability of the molten film, it is preferable that the melt mass flow rate (measured in accordance with ISO 1133 under the conditions of 260 ° C. and 98.07 N) is 0.1 to 20 g / 10 min. it can. The melt mass flow rate is more preferably 0.5 to 10 g / 10 min. Further, the glass transition temperature of the poly (meth) acrylimide resin is preferably 150 ° C. or higher from the viewpoint of heat resistance. More preferably, it is 170 degreeC or more.

The poly (meth) acrylimide resin may be a thermoplastic resin other than the poly (meth) acrylimide resin; a pigment, an inorganic filler, an organic filler, and a resin filler, as long as it does not contradict the purpose of the present invention. An additive such as a lubricant, an antioxidant, a weather resistance stabilizer, a heat stabilizer, a mold release agent, an antistatic agent, and a surfactant may be further included. The blending amount of these optional components is usually about 0.01 to 10 parts by mass when the poly (meth) acrylimide resin is 100 parts by mass.

Commercial examples of the poly (meth) acrylimide resin include “PLEXIMID TT50 (product name)” and “PLEXIMID TT70 (product name)” manufactured by Evonik.

The poly (meth) acrylimide resin film is preferably a first poly (meth) acrylimide resin layer (α1); an aromatic polycarbonate resin layer (β); a second poly (meth) acrylimide resin. Layer (α2); is a transparent multilayer film directly laminated in this order. In the present specification, the present invention will be described on the assumption that the touch surface is formed on the α1 layer side.

Poly (meth) acrylimide resin is excellent in heat resistance and surface hardness, but machinability tends to be insufficient, whereas aromatic polycarbonate resin is excellent in machinability, Heat resistance and surface hardness tend to be insufficient. Therefore, by using the transparent multilayer film having the above-mentioned layer structure, it is possible to easily obtain a hard coat laminated film that compensates for the weaknesses of both and is excellent in any of heat resistance, surface hardness, and cutting workability. .

The layer thickness of the α1 layer is not particularly limited, but is usually 20 μm or more, preferably 40 μm or more, more preferably 60 μm or more, and still more preferably 80 μm or more, from the viewpoint of heat resistance and surface hardness of the hard coat laminated film of the present invention. It may be.

The layer thickness of the α2 layer is not particularly limited, but is preferably the same layer thickness as the α1 layer from the viewpoint of curl resistance of the hard coat laminated film of the present invention.

Here, the “same layer thickness” should not be interpreted as the same layer thickness in a physicochemically strict sense. It should be construed that the layer thickness is the same within the range of process and quality control that is usually performed industrially. This is because the curl resistance of the multilayer film can be kept good if the layer thickness is the same within the range of the amplitude of process and quality control that is usually performed industrially. In the case of an unstretched multilayer film by the T-die coextrusion method, since the process and quality are usually controlled with a width of about -5 to +5 μm, the layer thicknesses of 65 μm and 75 μm should be interpreted as the same. is there.

The layer thickness of the β layer is not particularly limited, but may be usually 20 μm or more, preferably 80 μm or more from the viewpoint of cutting resistance of the hard coat laminated film of the present invention.

The poly (meth) acrylimide resin used for the α1 layer and the α2 layer has been described above.

The poly (meth) acrylimide-based resin used for the α1 layer and the poly (meth) acrylimide-based resin used for the α2 layer have different resin characteristics, for example, poly (meth) with different melt mass flow rate and glass transition temperature. A (meth) acrylimide resin may be used, but from the viewpoint of curl resistance of the hard coat laminated film of the present invention, it is preferable to use one having the same resin characteristics. For example, using the same lot of the same grade is one preferred embodiment.

Examples of the aromatic polycarbonate resin used for the β layer include aromatic dihydroxy compounds such as bisphenol A, dimethylbisphenol A, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, and phosgene. A polymer obtained by an interfacial polymerization method with an aromatic dihydroxy compound such as bisphenol A, dimethyl bisphenol A, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, and carbonic acid such as diphenyl carbonate. One or a mixture of two or more aromatic polycarbonate resins such as a polymer obtained by a transesterification reaction with a diester can be used.

As a preferable optional component that can be included in the aromatic polycarbonate-based resin, a core-shell rubber can be exemplified. When the total of the aromatic polycarbonate-based resin and the core-shell rubber is 100 parts by mass, the core-shell rubber is 0-30 parts by mass (aromatic polycarbonate-based resin 100-70 parts by mass), preferably 0-10 parts by mass (aromatic By using it in an amount of 100 to 90 parts by mass of a polycarbonate-based resin, it is possible to further improve cutting resistance and impact resistance.

Examples of the core shell rubber include methacrylic acid ester / styrene / butadiene rubber graft copolymer, acrylonitrile / styrene / butadiene rubber graft copolymer, acrylonitrile / styrene / ethylene / propylene rubber graft copolymer, and acrylonitrile / styrene / acrylic. Examples thereof include core-shell rubbers such as an acid ester graft copolymer, a methacrylic ester / acrylic ester rubber graft copolymer, and a methacrylic ester / acrylonitrile / acrylic ester rubber graft copolymer. As said core shell rubber, these 1 type, or 2 or more types of mixtures can be used.

The aromatic polycarbonate-based resin may be a thermoplastic resin other than the aromatic polycarbonate-based resin and the core-shell rubber; a pigment, an inorganic filler, an organic filler, a resin filler; An additive such as an antioxidant, a weather resistance stabilizer, a heat stabilizer, a mold release agent, an antistatic agent, and a surfactant may be further included. The compounding amount of these optional components is usually about 0.01 to 10 parts by mass when the total of the aromatic polycarbonate resin and the core-shell rubber is 100 parts by mass.

The production method of the poly (meth) acrylimide resin film (including the case where the film is the transparent multilayer film) is not particularly limited. As a preferable production method, methods described in JP-A-2015-033844 and JP-A-2015-034285 can be exemplified.

Further, when forming the second hard coat, in order to increase the adhesive strength with the second hard coat on the hard coat forming surface or both surfaces of the poly (meth) acrylimide resin film or the transparent multilayer film, a corona is previously used. Easy adhesion treatment such as discharge treatment or anchor coat formation may be performed.

The hard coat laminated film of the present invention preferably has the first hard coat, the second hard coat, the layer of the transparent resin film, and the third hard coat in order from the surface side. By forming the third hard coat, both the force to curl the hard coat laminated film to one side (hereinafter sometimes abbreviated as curl force) and the force to curl to the other work both. become. The occurrence of curling can be suppressed by canceling these two curling forces to zero.

In recent years, for the purpose of reducing the weight of an image display device, a two-layer touch panel (so-called one glass solution) in which a touch sensor is directly formed on the back side of a display face plate has been proposed. In order to further reduce the weight, a one plastic solution that replaces the so-called one glass solution has been proposed. When the hard coat laminated film of the present invention is used for a one plastic solution that replaces the so-called one glass solution, the above-mentioned third hard coat is formed to give suitable characteristics as a printing surface. Becomes easier.

The hard coat laminated film of this invention may have arbitrary layers other than the said 1st hard coat, the said 2nd hard coat, the layer of the said transparent resin film, and the said 3rd hard coat as needed. Examples of the optional layer include a hard coat other than the first to third hard coats, an anchor coat, an adhesive layer, a transparent conductive layer, a high refractive index layer, a low refractive index layer, and an antireflection functional layer. be able to.

Production method:
The manufacturing method in particular of the hard coat laminated film of this invention is not restrict | limited, It can manufacture by arbitrary methods. As a preferable production method, from the viewpoint of adhesion between the first hard coat and the second hard coat, for example,
(1) A step of forming a wet coating film made of the second hard coat forming paint on the transparent resin film;
(2) The wet coating film made of the second hard coat forming paint has an active energy ray with an integrated light amount of 1 to 230 mJ / cm ² , preferably 5 to 200 mJ / cm ² , more preferably 10 to 160 mJ / cm. ² , more preferably 20 to 120 mJ / cm ² , most preferably 30 to 100 mJ / cm ^2, and the wet coating film made of the second hard coat forming paint is applied in a dry-to-touch state. Forming a film;
(3) forming a wet paint film made of the first hard coat forming paint on the touch-dried paint film made of the second hard coat forming paint; and (4) the first The wet coating film comprising a hard coat forming coating is preheated to a temperature of 30 to 100 ° C., preferably 40 to 85 ° C., more preferably 50 to 75 ° C., and the active energy ray is integrated to 240 to 10,000 mJ / cm. ² , preferably 320 to 5000 mJ / cm ² , more preferably 360 to 2000 mJ / cm ² . I can give you a way.

In the step (1), the method for forming the wet coating film composed of the second hard coat forming coating is not particularly limited, and a known web coating method can be used. Specifically, methods such as roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, and die coating can be used.

The wet coating film made of the second hard coat forming paint formed in the step (1) becomes dry to the touch or has no tackiness in the step (2) and directly touches the web device. However, handling problems such as sticking will no longer occur. Therefore, in the next step (3), a wet paint film made of the first hard coat forming paint is formed on the touch-dried paint film made of the second hard coat forming paint. Will be able to.

In this specification, “the coating film is in a dry-to-touch state (without tackiness)” means that there is no problem in handling even when the coating film directly touches the web device. .

Irradiation with active energy rays in the step (2) depends on the characteristics of the paint used as the second hard coat-forming paint, but from the viewpoint of ensuring that the paint film is dry to the touch, the integrated light quantity is usually 1 J. / cm ² or more, preferably 5 mJ / cm ² or more, more preferably 10 mJ / cm ² or more, more preferably 20 mJ / cm ² or more, and most preferably carried out such that 30 mJ / cm ² or more. On the other hand, from the viewpoint of adhesion between the first hard coating and second hard coating, integrated light quantity usually 230 mJ / cm ² or less, preferably 200 mJ / cm ² or less, more preferably 160 mJ / cm ² or less, more preferably 120mJ / Cm ² or less, most preferably 100 mJ / cm ² or less.

In the step (2), it is preferable to pre-dry the wet coating film made of the second hard coat forming coating material before irradiating the active energy ray. In the preliminary drying, for example, the time required for the web to pass from the inlet to the outlet in the drying furnace set at a temperature of about 23 to 150 ° C., preferably 50 to 120 ° C. is about 0.5 to 10 minutes. , Preferably by passing at a line speed of 1 to 5 minutes.

When the active energy ray is irradiated in the step (2), the wet coating film made of the second hard coat forming coating material may be preheated to a temperature of 40 to 120 ° C, preferably 70 to 100 ° C. The coated film can be surely brought into a dry-to-touch state. The preheating method is not particularly limited, and can be performed by any method. An example of a specific method will be described later in the description of step (4) below.

In the step (3), the method for forming the wet coating film made of the first hard coat forming paint is not particularly limited, and a known web coating method can be used. Specifically, methods such as roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, and die coating can be used.

The wet coating film made of the first hard coat forming paint formed in the step (3) is completely cured in the step (4). At the same time, the coating film made of the second hard coat forming coating is also completely cured.

Although not intended to be bound by theory, it is possible to improve the adhesion between the first hard coat and the second hard coat by the method described above. Then, it is sufficient to make the coating film dry to the touch, but it is suppressed to an integrated light amount that is insufficient for complete curing, and an integrated light amount sufficient to completely cure the coating film for the first time in the above step (4). It is assumed that complete curing of both hard coats is achieved simultaneously.

In the step (4), the irradiation with active energy rays is preferably 240 mJ / cm ² or more from the viewpoint of complete curing of the coating film and the adhesion of the first hard coat and the second hard coat. the 320 mJ / cm ² or more, more preferably carried out so that 360 mJ / cm ² or more. On the other hand, in view to obtain a hard coat laminated film are prevented from becoming those yellowing, and from the viewpoint of cost, integrated light quantity 10000 mJ / cm ² or less, preferably 5000 mJ / cm ² or less, more preferably 2000 mJ / cm ² Perform as follows.

In the step (4), it is preferable to pre-dry the wet coating film made of the first hard coat forming paint before irradiating the active energy ray. In the preliminary drying, for example, the time required for the web to pass from the inlet to the outlet in the drying furnace set at a temperature of about 23 to 150 ° C., preferably 50 to 120 ° C. is about 0.5 to 10 minutes. , Preferably by passing at a line speed of 1 to 5 minutes.

When irradiating active energy rays in the step (4), the wet coating film made of the first hard coat forming paint has characteristics of the first hard coat forming paint and the second hard coat forming paint. From the viewpoint of obtaining good interlayer adhesion strength even when the temperature is greatly different, the temperature is preheated to 30 to 100 ° C, preferably 40 to 85 ° C, more preferably 50 to 75 ° C. The preheating method is not particularly limited, and can be performed by any method. For example, as shown in FIG. 1, a method of controlling the surface temperature of the roll to a predetermined temperature by holding the web on a roll facing the active energy ray irradiation apparatus; surrounding the active energy ray irradiation apparatus as an irradiation furnace; A method of controlling the temperature to a predetermined temperature; and combinations thereof.

After the step (4), an aging process may be performed. The characteristics of the hard coat laminated film can be stabilized.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these.

Measurement method (a) Total light transmittance:
According to JIS K 7361-1: 1997, it measured using the turbidimeter "NDH2000 (brand name)" of Nippon Denshoku Industries Co., Ltd.

(B) Pencil hardness:
According to JIS K 5600-5-4, under the condition of 750 g load, the pencil “Uni (trade name)” of Mitsubishi Pencil Co., Ltd. was used to measure the first hard coat surface of the hard coat laminated film.

(C) Haze;
According to JIS K 7136: 2000, it measured using the turbidimeter "NDH2000 (brand name)" of Nippon Denshoku Industries Co., Ltd.

(D) Minimum bending radius:
JIS-K6902: With reference to the bending formability of 2007 (Method B), the test piece conditioned for 24 hours at a temperature of 23 ° C. ± 2 ° C. and a relative humidity of 50 ± 5% was bent at a temperature of 23 ° C. ± 2 ° C. The lines were formed in a direction perpendicular to the machine direction of the hard coat laminated film, and bent so that the first hard coat of the hard coat laminated film was on the outer side to form a curved surface. Among the forming jigs in which no cracks occurred, the radius of the front part of the smallest front part radius was defined as the minimum bending radius. This “front portion” means the same term relating to a forming jig in the method B defined in JIS K6902: 2007, section 18.2.

(E) Water contact angle:
A method of calculating the first hard coat surface of the hard coat laminated film from the width and height of water droplets using an automatic contact angle meter “DSA20 (trade name)” manufactured by KRUS (see JIS R 3257: 1999). Measured with

(F) Scratch resistance 1 (water contact angle after cotton wiping):
JIS L is a test piece that is 150 mm long and 50 mm wide and is sampled so that the machine direction of the hard coat laminated film is the vertical direction of the test piece so that the first hard coat of the hard coat laminated film is on the surface. A stainless steel plate (10 mm long, 10 mm wide, 1 mm thick) placed on the Gakushin Tester No. 0849 and covered with 4 layers of gauze (Kawamoto Sangyo Co., Ltd. medical type 1 gauze) , Set the stainless steel plate so that the vertical and horizontal surfaces are in contact with the test piece, place a 350 g load, and place the first hard coat surface of the test piece on the condition that the moving distance of the friction terminal is 60 mm and the speed is 1 reciprocation / second. After rubbing 10,000 times, the water contact angle of the cotton swab was measured according to the above method (e). When the water contact angle is 100 degrees or more, after reciprocating 5,000 times, according to the method of (e) above, the work of measuring the water contact angle of the cotton wiping location was repeated and evaluated according to the following criteria: .
A: Water contact angle of 100 degrees or more even after 25,000 round trips.
B: Water contact angle is 100 degrees or more after 20,000 round trips, but less than 100 degrees after 25,000 rounds.
C: Water contact angle is 100 degrees or more after 15,000 round trips, but less than 100 degrees after 20,000 rounds.
D: Water contact angle is 100 degrees or more after 10,000 round trips, but less than 100 degrees after 15,000 rounds.
E: Water contact angle less than 100 degrees after 10,000 round trips.

(G) Scratch resistance 2 (steel wool resistance)
The hard coat laminated film was placed on a JIS L 0849 Gakushin Tester so that the first hard coat was the surface. Subsequently, after # 0000 steel wool was attached to the friction terminal of the Gakushin Tester, a 500 g load was placed, and the surface of the test piece was rubbed 100 times back and forth, and then the friction part was visually observed. In the case where no scratch was observed, after further rubbing 100 times, the work of visually observing the friction part was repeated and evaluated according to the following criteria.
A: No scratches are observed even after 500 round trips.
B: No scratches are observed after 400 round trips, but scratches can be observed after 500 round trips.
C: Scratches are not recognized after 300 round trips, but can be recognized after 400 round trips.
D: Scratches are not recognized after 200 round trips, but can be recognized after 300 round trips.
E: Scratches are not recognized after 100 reciprocations, but can be recognized after 200 reciprocations.
F: Scratches can be recognized after 100 reciprocations.

(H) Yellowness index;
In accordance with JIS K 7105: 1981, the measurement was performed using a chromaticity meter “SolidSpec-3700 (trade name)” manufactured by Shimadzu Corporation.

(I) Surface smoothness (surface appearance):
The surface (both surfaces) of the hard coat laminated film was visually observed while being applied with various incident angles of the fluorescent light, and evaluated according to the following criteria.
A: There is no wave or scratch on the surface. There is no cloudiness even when looking at the light up close.
○: There is a part with a slight cloudiness when looking closely at the light.
Δ: Slight swells and scratches are observed on the surface when viewed closely. There is also a cloudiness.
X: Many undulations and scratches can be observed on the surface. There is also a clear cloudiness.

(Nu) Cross cut test (adhesion):
In accordance with JIS K 5600-5-6: 1999, 100 square cuts (1 square = 1 mm × 1 mm) from the first hard coat surface side were put into the hard coat laminated film, and then the adhesion test tape was applied to the grid. After pasting and squeezing with fingers, it was peeled off. Evaluation criteria were in accordance with Table 1 of the above JIS standard.
Classification 0: The edges of the cuts are completely smooth, and there is no peeling in any lattice eye.
Classification 1: Small peeling of the coating film at the intersection of cuts. It is clearly not more than 5% that the crosscut is affected.
Classification 2: The coating film is peeled along the edge of the cut and / or at the intersection. The cross-cut portion is clearly affected by more than 5% but not more than 15%.
Classification 3: The coating film is partially or completely peeled along the edge of the cut, and / or various parts of the eyes are partially or completely peeled off. The cross-cut portion is clearly affected by more than 15% but not more than 35%.
Classification 4: The coating film is partially or completely peeled along the edge of the cut, and / or some eyes are partially or completely peeled off. The cross-cut portion is clearly affected by more than 35% but not more than 65%.
Category 5: When the degree of peeling exceeds Category 4.

(L) Cutting workability (state of curved cutting line):
Using a router machine that is automatically controlled by a computer, a hard-coated laminated film was provided with a true circular cutting hole with a diameter of 2 mm and a true circular cutting hole with a diameter of 0.5 mm. The mill used at this time was a four-blade made of cemented carbide with a rounded tip at the tip of the cylinder, with a nick, and the blade diameter was appropriately selected according to the machining location. Then, about the cutting hole of diameter 2mm, the cutting end surface was observed visually or a microscope (100 times), and the following references | standards evaluated. Similarly, about the cutting hole of diameter 0.5mm, the cutting end surface was observed visually or microscope (100 times), and the following references | standards evaluated. The table shows the former results-the latter results in this order.
A: No cracks or whiskers are observed even under microscopic observation. O: No cracks are observed even under microscopic observation. But beards are allowed.
(Triangle | delta): A crack is not recognized visually. However, cracks are observed by microscopic observation.
X: Cracks are recognized visually.

(E) Shrinkage start temperature (heat-resistant dimensional stability):
From the temperature-test piece length curve measured according to JIS K 7197: 1991, the change of the test piece length from increase (expansion) to decrease (shrinkage) on the lowest temperature side in the range of 20 ° C. to the glass transition temperature of the raw material resin. The inflection point (temperature at which the length of the test piece becomes maximum) was calculated as the shrinkage start temperature. For the measurement, a thermomechanical analyzer (TMA) “EXSTAR 6100 (trade name)” manufactured by Seiko Instruments Inc. was used. The test piece was 20 mm long and 10 mm wide, and the film was collected so that the machine direction (MD) of the film was the vertical direction of the test piece. Conditioning of the test piece was performed at a temperature of 23 ° C. ± 2 ° C. and a relative humidity of 50 ± 5% for 24 hours. For the purpose of measuring the dimensional stability as a physical property value of the film, the condition adjustment at the maximum measurement temperature was not performed. . The distance between chucks was 10 mm, and the tensile load was 4.0 mN / mm ² . The temperature program was a program for holding the temperature at 20 ° C. for 3 minutes and then increasing the temperature to 300 ° C. at a temperature increase rate of 5 ° C./min.

Raw materials used (A) Multifunctional (meth) acrylate:
(A-1) Dipentaerythritol hexaacrylate. 6 sensuality.
(A-2) Pentaerythritol triacrylate. Trifunctional.

(B) Water repellent:
(B-1) An acryloyl group-containing fluoropolyether water repellent “KY-1203 (trade name)” from Shin-Etsu Chemical Co., Ltd. Solid content 20% by weight.
(B-2) Solvay's methacryloyl group-containing fluoropolyether water repellent “FOMBLIN MT70 (trade name)”. Solid content 70% by weight.

(C) Silane coupling agent:
(C-1) N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane “KBM-602 (trade name)” from Shin-Etsu Chemical Co., Ltd.
(C-2) N-2- (aminoethyl) -3-aminopropyltrimethoxysilane “KBM-603 (trade name)” from Shin-Etsu Chemical Co., Ltd.
(C-3) 3-aminopropyltrimethoxysilane “KBM-903 (trade name)” of Shin-Etsu Chemical Co., Ltd.
(C-4) 3-Mercaptopropylmethyldimethoxysilane “KBM-802 (trade name)” of Shin-Etsu Chemical Co., Ltd.
(C-5) 3-glycidoxypropyltrimethoxysilane “KBM-403 (trade name)” manufactured by Shin-Etsu Chemical Co., Ltd.

(D) Inorganic fine particles having an average particle size of 1 to 300 nm:
(D-1) Silica fine particles having an average particle diameter of 20 nm and surface-treated with a silane coupling agent having a vinyl group.

(E) Leveling agent:
(E-1) Silicon-acrylic copolymer leveling agent “Disparon NSH-8430HF (trade name)” from Enomoto Kasei Co., Ltd. Solid content 10% by weight.
(E-2) Silicon / acrylic copolymer leveling agent “BYK-3550 (trade name)” of Big Chemie Japan Co., Ltd. Solid content 52% by weight.
(E-3) An acrylic polymer leveling agent “BYK-399 (trade name)” of Big Chemie Japan Co., Ltd. Solid content 100 mass%.
(E-4) Silicone leveling agent “Disparon LS-480 (trade name)” from Enomoto Kasei Co., Ltd. Solid content 100 mass%.

(F) Optional component:
(F-1) Phenylketone-based photopolymerization initiator (1-hydroxycyclohexyl phenyl ketone) “SB-PI714 (trade name)” of Sojyo Sangyo Co., Ltd.
(F-2) 1-methoxy-2-propanol.

(H1) First hard coat forming paint:
(H1-1) 100 parts by mass of (A-1), 2 parts by mass of (B-1) (0.40 parts by mass in terms of solid content), 0.06 parts by mass of (B-2) (in terms of solid content) 0.042 parts by mass), (C-1) 0.5 parts by mass, (F-1) 4 parts by mass, and (F-2) 100 parts by mass of paint obtained by mixing and stirring. Table 1 shows the recipe. In addition, about the said (B-1) and the said component (B-2), the value of solid content conversion is described in the table | surface.

(H1-2 to 15) A paint was obtained in the same manner as in (H1-1) except that the formulation was changed as shown in Table 1 or Table 2.

(H1 ′) Comparative first hard coat forming paint:
(H1′-1) A paint was obtained in the same manner as in the above (H1-1) except that the formulation was changed as shown in Table 1.

(H2) Second hard coat forming paint:
(H2-1) 100 parts by mass of (A-2), 140 parts by mass of (D-1), 2 parts by mass of (E-1) (0.2 parts by mass in terms of solid content), (F-1) ) A paint obtained by mixing and stirring 17 parts by mass and 200 parts by mass of the above (F-2). Table 3 shows the recipe. In addition, about said (E-1), the value of solid content conversion is described in the table | surface.

(H2-2 to 13) A paint was obtained in the same manner as (H2-1) except that the formulation was changed as shown in Table 3 or Table 4.

(H2 ′) Comparative second hard coat forming coating:
A paint was obtained in the same manner as in the above (H2-1) except that the formulation of (H2′-1) was changed as shown in Table 4.

(P) Transparent resin film:
(P-1) Two types, three layers, a multi-manifold type co-extrusion T-die, and a device equipped with a winder equipped with a mechanism for pressing a molten film with a mirror roll and a mirror belt are used. Evonik's poly (meth) acrylimide “PLEXIMID TT50 (trade name)” as both outer layers (α1 layer and α2 layer) of the multilayer resin film, and aromatic of Sumika Stylon Polycarbonate Co., Ltd. as the intermediate layer (β layer) Polycarbonate “Caliver 301-4 (trade name)” is continuously co-extruded from the co-extrusion T-die and circulated along the rotating mirror surface roll and the outer peripheral surface of the mirror surface roll so that the α1 layer is on the mirror surface roll side. A transparent resin film having a total thickness of 250 μm, an α1 layer thickness of 80 μm, a β layer thickness of 90 μm, and an α2 layer thickness of 80 μm. Obtained. At this time, the setting conditions were T-die set temperature 300 ° C., mirror roll set temperature 130 ° C .; mirror belt set temperature 120 ° C., take-up speed 6.5 m / min.

(P-2) A transparent resin film was obtained in the same manner as in the above (P-1) except that the layer ratio was changed to an α1 layer thickness of 60 μm, a β layer thickness of 130 μm, and an α2 layer thickness of 60 μm. It was.

(P-3) A transparent resin film was obtained in the same manner as in the above (P-1) except that the layer ratio was changed to 40 μm for the α1 layer, 170 μm for the β layer, and 40 μm for the α2 layer. It was.

(P-4) A biaxially stretched polyethylene terephthalate film “Diafoil (trade name)” manufactured by Mitsubishi Plastics, Inc., having a thickness of 250 μm.

(P-5) Acrylic resin film “Technoloy S001G (trade name)” from Sumitomo Chemical Co., Ltd., thickness 250 μm.

(P-6) Aromatic polycarbonate of Sumika Stylon Polycarbonate Co., Ltd. using a single-layer T-die and a device equipped with a winder equipped with a mechanism for pressing a molten film with a mirror roll and a mirror belt. Caliber 301-4 (trade name) "is continuously extruded from a T-die, and fed between a rotating mirror surface roll and a mirror surface belt circulating along the outer peripheral surface of the mirror surface roll, and pressed to have a total thickness of 250 μm. A transparent resin film was obtained. At this time, the setting conditions were T-die set temperature 320 ° C., mirror roll set temperature 140 ° C .; mirror belt set temperature 120 ° C., take-up speed 5.6 m / min.

Example 1
Corona discharge treatment was performed on both sides of (P-1). The wetness index on both sides was 64 mN / m. Next, the above (H2-1) was applied on the surface of the α1 layer side so as to have a wet thickness of 40 μm (thickness after curing: 22 μm) using a die-type coating apparatus. Next, after passing the drying oven set at a furnace temperature of 90 ° C. at a line speed of 1 minute to pass from the inlet to the outlet, the high pressure mercury lamp type ultraviolet irradiation device and the diameter of 25.4 cm Using a curing device in which a mirror metal roll was placed (see FIG. 1), the mirror metal roll was processed at a temperature of 90 ° C. and an integrated light intensity of 80 mJ / cm ² . The wet coating film of (H2-1) was a touch-dried coating film. Next, using a die-type coating apparatus on the (H2-1) touch-dried coating film, the (H1-1) is made to have a wet thickness of 4 μm (post-curing thickness: 2 μm). Applied. Next, after passing the drying furnace set at a furnace temperature of 80 ° C. at a line speed of 1 minute to pass from the inlet to the outlet, the high pressure mercury lamp type ultraviolet irradiation device and the diameter of 25.4 cm Using a curing device facing the mirror surface metal roll (see FIG. 1), processing is performed under the conditions of a mirror surface metal roll temperature of 60 ° C. and an integrated light amount of 480 mJ / cm ² to form a first hard coat and a second hard coat. did. Subsequently, the third hard coat is applied on the surface of the α2 layer side, and the same paint as that used for forming the second hard coat (Example 1 is (H2-1) above) is used to apply the die method. Using an apparatus, it was formed to a thickness of 22 μm after curing to obtain a hard coat laminated film. The above tests (i) to (wo) were conducted. The results are shown in Table 5.

Examples 2-30, Examples 1-4C
Except that at least any one of the coating material (α), the coating material (β), and the transparent resin film to be used was changed as shown in any one of Tables 5 to 9, all were performed in the same manner as in Example 1. The results are shown in any one of Tables 5-9.

Examples 31-53
It carried out similarly to Example 1 except having changed the manufacturing conditions of the hard coat laminated film as shown in any one of Tables 10-13. The results are shown in any one of Tables 10-13.

The hard coat laminated film of the present invention is excellent in transparency, color tone, scratch resistance, surface hardness, and surface appearance. Therefore, it can be suitably used as a display face plate of an image display device having a touch panel function.

It is a conceptual diagram of the ultraviolet irradiation device used in the Example. It is a conceptual diagram of the section which shows an example of the hard coat lamination film of the present invention. It is a figure explaining a curvature radius.

1: UV irradiation device 2: Mirror surface metal roll 3: Web 4: Holding angle 5: First hard coat 6: Second hard coat 7: First poly (meth) acrylimide resin layer (α1)
8: Aromatic polycarbonate resin layer (β)
9: Second poly (meth) acrylimide resin layer (α2)
10: Third hard coat

Claims (10)

The first hard coat, the second hard coat, and the transparent resin film layer in order from the surface side,
The first hard coat is made of a coating containing no inorganic particles;
The second hard coat is made of a coating containing inorganic particles;
A hard coat laminated film satisfying the following (a) and (b).
(A) The total light transmittance is 85% or more.
(B) The pencil hardness of the first hard coat surface is 5H or more.
The hard coat laminated film according to claim 1, wherein the first hard coat surface has a pencil hardness of 7H or more.
Furthermore, the hard coat laminated film of Claim 1 or 2 which satisfies the following (c) and (d).
(C) Haze is 2.0% or less.
(D) The minimum bending radius is 40 mm or less.
The hard coat laminated film according to any one of claims 1 to 3, further satisfying the following (e) and (f).
(E) The water contact angle on the surface of the first hard coat is 100 degrees or more.
(F) The water contact angle after 20,000 swabs on the first hard coat surface is 100 degrees or more.
The transparent resin film is
First poly (meth) acrylimide resin layer (α1);
Aromatic polycarbonate-based resin layer (β);
A second poly (meth) acrylimide resin layer (α2);
It is a transparent multilayer film laminated | stacked in this order, The hard coat laminated film of any one of Claims 1-4.
The first hard coat comprises a paint containing a silane coupling agent;
The hard coat laminated film of any one of Claims 1-5.
The thickness of the said 1st hard coat is 0.5-5 micrometers, The hard coat laminated film of any one of Claims 1-6.
The hard coat laminated film according to any one of claims 1 to 7, wherein the second hard coat has a thickness of 15 to 30 µm.
Use of the hard coat laminated film according to any one of claims 1 to 8 as an image display device member.
The image display apparatus containing the hard-coat laminated | multilayer film of any one of Claims 1-8.